Production of metal sulfonates



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UNITED srArss PATENT} OFFICE nonuo'nox or METAL sunrom'ras Felix c. emu, Philadelphia, Pa., mumto The Atlantic Beilning Company,

Philadelphia,

Pa., a corporation of Pennsylvania N Drawing.

oil-soluble. sulfonic acid is reacted with a cyclic.

nitrogen base and the resulting sulfonate is heated in admixture with a basic compound of a metal at such temperature and for a sufllcient period of time to drive 011. the cyclic nitrogen base and replace same with the metal, thus producing the desired metal sulfonate.

The cyclic nitrogen base sulfonates employed in the first step of. my process are prepared by reacting oil-soluble sulfonic acids with a cyclic nitrogen base in an amount sufllcient to at least partially neutralize the sulfonic acids, and preferably to completely neutralize the acids. The oilsoluble sulfonic acids may be derived from petroleum oils, heavy coal tar distillates. fats, fatty oils, and the like by subjecting the raw material to treatment with a sulfonating agent such as concentrated sulfuric acid, fuming sulfuric acid, chlorsulfonic acid, or sulfur trioxide for aperiod of time suillcient to eiIect sulfonatlon, and thereafter separating insoluble sludge from the oil containing the sulfonic acids. tion of sulfonic acids is then neutralized with the cyclic nitrogen base to form a relatively insoluble cyclic nitrogen base sulfonate which may be separated i'rom the oil by decantation or centrifuging. The cyclic nitrogen bases which may be employed are exemplified by pyridine, the alkyl-substituted pyridines such as the methyl and ethyl pyridines (lutidines), quinoline, the alkyl-substituted quinolines (quinaldines), isoquinoline, piperidine,

yridazine, py-razole, pyrazine, pyrrole, or mixtures of two or more thereof. In preparing the cyclic nitrogen base sulfonate, there is added to the oil containing the sulfonic acids, an amount of nitrogen base calculated to give 90 per cent to 100 per cent neutralization of the sulfonic acids,

Application Serial No. 618,0

4 Claims. (01480-448) 7 the sulfonate begins to precipitate and settle, and

the temperature is then reduced to 140 F. to 160 F. and the oil is decanted from the sulfonate at this temperature. If desired, the sulfonate may be centrifugally separated from the oil, provided the temperature is maintained suillciently high to prevent solidification of the sulfonate. At temperatures between 140 F. and 220 F. the sulfonate, which normally occludes some oil, is a vis-' cous material which will flow at such temperature, but at ordinary temperatures (70 F.) the sulfonate is solid. While it is preferred to eflect separation of the sulfonate from the oil at elevated temperatures, it is of course possible to accomplish such result at ordinary temperatures, provided a sufllciently long settling period is employed, In the case of sulfonates prepared from I relatively heavy oils or high boiling naphthenic The oil soluoils, the precipitation of the sulfonates and the settling thereof from the oil may be facilitated by the addition of a small amount of water, for example, 1 per cent to 3 per cent by volume of the oil. If it is desired to prepare a sulfonate substan-' tially free of oil or containing a controlled amount of oil, the crude sulfonate may be deoiled by treatment with a parafflnic hydrocarbon solvent, such as straight-run low boiling naphtha, pentane, butane, liquid propane, or mixtures thereof, in which the oil is soluble and the sulfonate relatively insoluble.

The cyclic nitrogen base sulfonate, as prepared above, is then converted to a metal sulfonate by adding a basic compound of a metal, such as the oxide, hydroxide, or carbonate, and the mixture is heated at a temperature sufficiently elevated to cause reaction, with the liberation and driving off of the cyclic nitrogen base and its replacement by the metal. This is accomplished at temperatures between 250 F. and 500 F'., and preferably between 300 F. and 400 F. The reaction temperature and duration of heating is dependent upon the nature of the cyclic nitrogen base,'its

and the mixture is thoroughly agitated for a peboiling point, and the pressure employed. At atmospheric pressure, a temperature between 300 F. and 400 F. has been found satisfactory in convetting pyridine and quinoline ,sulfon'ates into metal sulfonates. With a reduction in pressure, the temperature may be lowered. Alternatively, the reaction may be carried out in the presence of an inert gas, the sweeping action of which assists in the removal of the cyclic nitrogen base.

The metal bases which may be employed in accordance with this invention are exemplified by the oxides, hydroxides and carbonates of copper, cobalt, nickel, lead, tin, zinc, calcium,

strontium, barium, and aluminum. The quantity of \metal base employed should be suflicient to neutralize the sulfonic acid liberated from the cyclic nitrogen base sulfonate, and where it is desired to produce a basic sulfonate of the metal, a substantial excess of metal base is utilized. In a preferred mode of operation, freshly precipitated metal hydroxide is employed, since reaction is more rapid and complete than when the dry oxide, hydroxide, or carbonate is used. The reaction in many cases, may be facilitated by the addition of a small amount of water, for exampl up to 10 per cent by weight of the reactants.

The present invention may be further illustrated by the following examples. which, however, are not to be construed as limiting the scope thereof.

1. A selective solvent extract fraction of a petroleum lubricating 011 stock having a Saybolt universal viscosity of 524 seconds at 100 F. and an A. P. I. gravity oi 17.3 was treated with 5 successive dumps of 5 per cent by volume each of 98 per cent concentration sulfuric acid, the acid sludge being settled and separated between each dump. The resulting sour oil containing about 12 per cent of oil-soluble sulfonic acids was neutralized with a mixture of alkyl pyridines having a boiling range of 284 F. to 392 F. and a precipitate of viscous, dark colored pyridinium sulfonate was separated from the oil. This pyridinium sulfonate had a saponification number of 57.3.

100 parts by weight of the pyridinium sulfonate was admixed with 2.6 parts by weight of powdered aluminum hydroxide and the mixture was heated at 300 F. to 350 F. for 3 hours, a stream of air being passed over the reactants during the heat ing. As a result of the ensuing reaction the alkyl pyridines were driven 011 and replaced by the aluminum, and there was obtained a clear, sticky, semi-solid mass of aluminum tri-sulfonate which was soluble in benzene and extraction naphtha.

2. The procedure of Example 1 was repeated, with the exception that in the second step, '74 parts by weight of pyridinium sulfonate, 4 parts by weight of aluminum hydroxide, and 6 parts by weight of water were used. The resulting product appeared to be a sticky, semi-solid aluminum dihydroxy sulfonate.

3. To 10 parts by ing 12 per cent of oil-soluble sulionic acids was added 1 part by weight of quinoline, and the mixture was thoroughly agitated at about 80 F. until the reaction was completed. The mixture was then settled and a dark colored precipitate of quinolinium sulfonate was separated from the oil.

The quinolinium sulfonate was then mixed with sumcient freshly precipitated aluminum hydroxide to neutralize the sulfonic compound, and the mixture was heated at 425 F. for 3 hours in a stream of air. As a result of the reaction, quinoline was driven of! and replaced by the aluminum, and there was obtained a neutral aluminum sulfonate of the same character as that of Example 1.

To test the adhesivity-improving properties of the aluminum sulfonates as prepared above, road oils were made up comprising 34 per cent of furnace oil (medium), 61 per cent of /500 penetration asphalt, and 5 per cent of aluminum sulfonates. The road oils were added in increments to aggregate samples consisting of 100 grams of 7 20-60 mesh sand wetted with 50 grams of water, and it was found that despite the presence or the water, it required only 4.5 grams of each of the road oils for complete adhesion. These asphalt coated aggregates, when placed in boiling water weight of sour oil containit is possible to obtain concentrates containing upwards of 50 per cent of sulfonates, which, in the second step of the process are readily and economically converted into metal sulfonates, with regeneration of the cyclic nitrogen base which may be recycled for further use in the process.

I claim:

1. The method of producing a metal salt of an oil-soluble sulfonic acid, which comprises neutralizing an oil containing said oil-soluble sulionic acid with a heterocyclic nitrogen base at a temperature between 180 F. and 220 F., precipitating and separating the oil-insoluble nitrogen base sulfonate from the oil at a temperature between F. and F., and reacting the nitrogen base sulfonate with a basic compound of a metal at a temperature between 300 F. and 400 F. to replace the nitrogen base with the metal.

2. The method of producing a metal salt of an oil-soluble sulfonic acid, which comprises neutralizing an oil containing said oil-soluble sulfonic acid with pyridine at a temperature between 180 F. and 220 F., precipitating and separating the oil-insoluble pyridine sulfonate from the oil at a temperature between 140 F. and 160 F., and reacting the pyridine sulfonate with a basic compound of a metal at a temperature between 300 F. and 400 F. to replace the pyridine with the metal.

3. The method of producing a metal salt of an oil-soluble sulfonic acid, which comprises neutralizing an oil containing said oil-soluble sulfonic acid with uinoline at a temperature between 180 F. and 220 F., precipitating and separating the oil-insoluble quinoline sulfonate from the oil at a temperature between 140 F. and 160 F'., and reacting the quinoline sulfonate with a basic compound of a metal at a temperature between 300 F. and 400 F. to replace the quinoline with the metal.

4. The method of producing an aluminum salt of an oil-soluble sulfonic acid, which comprises neutralizing an oil containing said oil-soluble sulfonic acid with a heterocyclic nitro en base at a temperature between 180 F. and 220 F.. precipitating and separating the oil-insoluble nitrogen base sulfonate from the oil at a temperature between 140 F. and 160 F., and reacting the nitrogen base sulfonate with aluminum hydroxide at a temperature between 800 F. and 400 F. to replace the nitrogen base with aluminum.

. FELIX C. GZEMSKI.

REFERENCES CITED UNITED STATES PATENTS Num r Name Date 497.740 zeizler Mav 18. 1 93 709.821 Helmers S nt. 16. 1 2 1428.101 Divine I Dec. 5. 1 -2 1,495 R91 Divine II Mav 2'7. 1 .4 1,889,383 Schmidt Nov. 29, 1932 (Other references on following page) Number Number Number 6 Name 'Date Archibald et a1. Dec. 8, 1942 Potter Jan. 12, 1943 Colgate et a1 Apr. 13, 1943 FOREIGN PATENTS Country Date Great Britain Aug. 17, 1928 Germany June 2, 1932. 

